KR20140105540A - Phthalocyanine nano-size structures, and electronic elements using said nano-size structures - Google Patents

Abstract

And to provide an organic semiconductor material capable of producing an electronic device by a low-cost wet process. It is also an object of the present invention to provide an organic semiconductor electronic device which is difficult to break, lightweight, inexpensive, and high in characteristics.
It has been found by the present invention that an organic semiconducting material favorable to a wet process having improved performance can be provided by optimizing a phthalocyanine derivative constituting the phthalocyanine nano-sized structure, thereby completing the present invention. Further, by using the organic semiconductor material for the electronic device active portion (semiconductor layer), it is possible to provide an electronic device excellent in durability, hard to break, light in weight, inexpensive, and high in characteristics.

Description

PHTHALOCYANINE NANO-SIZE STRUCTURES, AND ELECTRONIC ELEMENTS USING SAID NANO-SIZE STRUCTURES BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to an electronic device comprising a phthalocyanine nano size structure, an ink composition containing the phthalocyanine nano size structure, an electronic device containing the phthalocyanine nano size structure, a transistor containing the phthalocyanine nano size structure in the channel portion, And a photoelectric conversion element containing the phthalocyanine nano size structure.

In recent years, there has been a demand for a " fragile, lightweight and inexpensive information terminal " that anyone can use at any place. In this realization, it is required to use a soft material having a cost merit in the transistor which is the key device (the most important element) of the information terminal. However, conventionally used inorganic materials such as silicon can not sufficiently meet such demands.

In this situation, "organic transistor (OFET)" which uses an organic compound (organic semiconductor) having a semiconductor characteristic for an active portion (semiconductor layer) of a transistor is attracting attention (see Non-Patent Document 1). Such organic semiconductors are capable of being subjected to low-temperature treatment flexibly and also have high affinity with solvents in general. Therefore, there is merit that a semiconductor layer can be manufactured (film-formed) at a low cost by using a wet process such as coating or printing on a flexible plastic substrate, which is indispensable for realization of "a fragile, lightweight and inexpensive information terminal" Is expected as a material for next-generation electronic devices.

Phthalocyanines are one of typical organic semiconductors and it is known that phthalocyanines exhibit good transistor characteristics by controlling a higher order structure, that is, the arrangement and aggregation state of molecules (see Non-Patent Document 2). However, since phthalocyanine derivatives have low solubility in solvents, it is difficult to manufacture devices by a wet process, and dry processes such as vacuum evaporation and sputtering are generally used when they are provided to electronic devices. Since such a dry process is a complicated and expensive process, it becomes difficult to provide a low-cost electronic device, which is one of the characteristics of organic semiconductors.

To solve this problem, there is disclosed a technique of manufacturing a transistor by a wet process by introducing a soluble substituent into the phthalocyanines and increasing solvent solubility (see Patent Document 1). However, in this method, since each molecule of the phthalocyanine species is not sufficiently arranged and the higher order structure can not be controlled, the transistor characteristics are inferior to those according to the dry process. In order to exhibit good semiconductor properties, it is important that each molecule has a crystal structure having dimensionality arranged in a certain direction. Therefore, it is important that a one-dimensional crystalline structure (long axis and long axis) ) Have come to expect.

On the other hand, in order to develop more favorably on an electronic device assuming a wet process, the one-dimensional crystalline structure is a one-dimensional crystalline structure having a short diameter of 500 nm or less (hereinafter referred to as a nano-sized one-dimensional structure) desirable.

Phthalocyanines are widely used as colorants for paints of printing inks, and many techniques for controlling their crystal sizes and shapes are well known. For example, there are a solvent salt milling method (see, for example, Patent Document 2) in which an inorganic salt and an organic solvent are mixed with a metal phthalocyanine to finely break the pigment into fine particles by a crusher (see, for example, Patent Document 2), and a method of dissolving the metal phthalocyanine in sulfuric acid And then precipitating in a large amount of water (see, for example, Patent Document 3). However, even using these methods, it was impossible to obtain a nano-sized structure comprising the phthalocyanine species as described above.

On the other hand, the present inventors have already disclosed a technology for producing a device by a wet process using a phthalocyanine nanowire using an unsubstituted phthalocyanine and a substituent-containing phthalocyanine (Patent Documents 4, 5 and 6 Reference). However, it is difficult to say that the phthalocyanine nanowire is completely optimized in terms of performance.

Japanese Patent Application Laid-Open No. 2008-303383 Japanese Patent Application Laid-Open No. 2002-121420 Japanese Patent Application Laid-Open No. 2004-091560 Japanese Patent Application Laid-Open No. 2009-280531 WO2010 / 122921 WO2011 / 065133

Advanced Materials 2002, No. 14, P.99 Applied Physics Letters 2005, 86, p. 22103

The present invention has been made in view of the above problems and aims to provide an organic semiconductor material capable of producing an electronic device by a low-cost wet process. In addition, it is intended to provide an organic semiconductor electronic device which is difficult to break, lightweight, inexpensive, and high in characteristics.

In order to achieve the above object, the inventors of the present invention have conducted intensive studies and found out that by optimizing a phthalocyanine derivative constituting a phthalocyanine nano-size structure, an organic semiconductor material favorable to a wet process having improved performance can be provided, The present invention has been completed. Further, by using the organic semiconductor material for an electronic device active portion (semiconductor layer), it has been found that an electronic device excellent in durability, less fragile, light in weight, inexpensive, and high in characteristics can be provided, .

That is,

A nano-sized structure containing an unsubstituted phthalocyanine and a phthalocyanine having a substituent,

The shape of the structure has a long diameter and a short diameter, a short diameter is 500 nm or less,

Wherein the unsubstituted phthalocyanine is represented by the general formula (1) or (2)

X is a group selected from the group consisting of a copper atom, a zinc atom, a cobalt atom, a nickel atom, a tin atom, a lead atom, a magnesium atom, an iron atom, a palladium atom, a calcium atom, GeO, TiO, VO, and AlCl Which is selected)

A phthalocyanine nano-sized structure wherein the phthalocyanine having a substituent is represented by the general formula (3) or (4).

X is a group selected from the group consisting of a copper atom, a zinc atom, a cobalt atom, a nickel atom, a tin atom, a lead atom, a magnesium atom, an iron atom, a palladium atom, a calcium atom, GeO, TiO, VO, and AlCl Which is selected,

Each hydrogen atom in the benzene ring of the phthalocyanine skeleton may be substituted with fluorine, chlorine, bromine, and Z ₁ to Z ₈ each independently represent a hydrogen atom, a noncyclic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent , A, b, c, and d each independently represent an integer of 0 to 4, provided that at least one of them is a divalent linking group selected from the group consisting of 0 , And when Z _{1 to} Z ₈ are the general formula (5) or (6), and both are hydrogen atoms.

(Wherein q is an integer of 4 to 100, each Q is independently a hydrogen atom or a methyl group, and Q 'is a non-cyclic hydrocarbon group having 1 to 30 carbon atoms)

(Wherein m is an integer of 1 to 20, and R and R 'each independently represent an alkyl group having 1 to 20 carbon atoms)

.

According to the present invention, since the phthalocyanine nano-sized structure according to the present invention is composed of phthalocyanine species rich in durability, a high number of electronic devices can be provided. Further, since the phthalocyanine nano-sized structure according to the present invention has better solvent dispersibility than the known phthalocyanine pigment microparticles, it is easy to form an ink composition, and thus a semiconductor layer is formed on a flexible plastic substrate by printing And it is possible to provide an electronic device that is difficult to break, lightweight, and inexpensive. In addition, the phthalocyanine nano-sized structure according to the present invention has higher controllability of the arrangement of phthalocyanine molecules throughout the structure than that of known phthalocyanine pigment microparticles, so that the semiconductor characteristics can be improved. The phthalocyanine nano-sized structure according to the present invention is a phthalocyanine nano-sized structure (nanowire) described in [Patent Document 4], [Patent Document 5] and [Patent Document 6] It is possible to provide an electronic device in which the semiconductor characteristics are improved and, as a result, the charge mobility (hereinafter simply referred to as a moving road mark) is improved.

1 is a schematic cross-sectional view of a photoelectric conversion element according to the present invention.
2 is a schematic cross-sectional view of a photoelectric conversion element according to the present invention.
3 is a schematic cross-sectional view of a transistor according to the present invention.
4 is a schematic plan view equivalent circuit diagram of a transistor array including a transistor according to the present invention.
5 is a graph showing the transmission electron microscopic image of the solid content in the dispersion (1) of the phthalocyanine nano size structure.
6 is a graph showing the transmission electron microscopic image of the solid content in the dispersion (2) of the phthalocyanine nano size structure.
FIG. 7 shows the transmission electron microscope image of the solid content in the dispersion (3) of the phthalocyanine nano size structure.
8 is a graph showing the transmission electron microscopic image of the solid content in the dispersion liquid (4) of the phthalocyanine nano size structure.

≪ Phthalocyanine nano size structure >

Hereinafter, the phthalocyanine nano size structure of the present invention will be described.

The phthalocyanine nano-sized structure of the present invention is a one-dimensional structure (wire-like, fiber-like, real, needle-like, rod-like or the like) structure having a long diameter and a short diameter (short axis) More preferably 300 nm or less, and most preferably 100 nm or less, and contains a phthalocyanine (phthalocyanine derivative) having an unsubstituted phthalocyanine and a substituent as structural constituent materials. As for the long diameter, there is no particular limitation if (long diameter / short diameter)> 1 (long diameter / short diameter is larger than 1). The mixing ratio of the unsubstituted phthalocyanine to the phthalocyanine having a substituent is preferably from 1 to 200 mass% (mass of phthalocyanine having a substituent x 100 / mass of unsubstituted phthalocyanine) relative to an unsubstituted phthalocyanine having a substituent %, More preferably from 1 to 120% by mass (later).

Examples of the unsubstituted phthalocyanine constituting the phthalocyanine nano size structure of the present invention include the phthalocyanine represented by the general formula (1) and the nonmetal phthalocyanine represented by the general formula (2).

In the general formula (1), X is not particularly limited as long as it forms phthalocyanine, and examples thereof include copper, zinc, cobalt, nickel, tin, lead, magnesium, iron, palladium, Metal oxides and metal halides such as GeO, TiO (titanyl), VO (vanadyl), and AlCl (aluminum chloride), among which copper atoms, zinc atoms and iron atoms are particularly preferable Do.

A feature of the phthalocyanine nano-sized structure of the present invention is that the phthalocyanine having a substituent is a phthalocyanine represented by the following general formula (3) or (4) wherein the hydrogen atom of the phthalocyanine skeleton is substituted with a sulfamoyl group (-SO ₂ NZZ ' Derivative (sulfamoyl group substituted phthalocyanine).

In the formula (3) or (4), X is at least one element selected from the group consisting of copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, iron atom, GeO, TiO, VO, and AlCl,

Each hydrogen atom in the benzene ring of the phthalocyanine skeleton may be substituted with fluorine, chlorine, bromine, and Z ₁ to Z ₈ each independently represent a hydrogen atom, a noncyclic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent , A, b, c, and d each independently represent an integer of 0 to 4, provided that at least one of them is a divalent linking group selected from the group consisting of 0 , And when Z _{1 to} Z ₈ are the general formula (5) or (6), and both are hydrogen atoms.

(Wherein q is an integer of 4 to 100, each Q is independently a hydrogen atom or a methyl group, and Q 'is a non-cyclic hydrocarbon group having 1 to 30 carbon atoms)

(Wherein m is an integer of 1 to 20, and R and R 'are each independently an alkyl group having 1 to 20 carbon atoms)

The non-cyclic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent may be either a linear hydrocarbon-derived or partially hydrocarbon-based hydrocarbon group, and the hydrocarbon group may be either a saturated hydrocarbon-containing or unsaturated hydrocarbon group. Examples of the noncyclic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- Butyl group, 1- (3-methyl) -butyl group, 2- (3-methyl) -butyl group, Ethylhexyl group, a 2-ethylhexyl group, a (2,2-dimethyl) -propyl group (also known as neopentyl group), a hexyl group, a n-hexyl group, a heptyl group, N-heptyl group, n-octadecyl group, n-octadecyl group, n-heptadecyl group, n-heptadecyl group, N-heptadecyl, n-heptadecyl, octadecyl, stearyl (n-octadecyl), nonadecyl, n-nonadecyl, n-hexadecyl, A tetracosyl group, a tetracosyl group, and a n-triacontyl group, and any hydrogen atom in the hydrocarbon group may be substituted with a hydrocarbon group Is optionally substituted is substituted with a substituent (late) of the possible known. Of these, from the viewpoint of semiconductor characteristics, the number of carbon atoms is preferably 25 or less, more preferably 22 or less.

Examples of the substituent include vinyl, 1-propenyl, allyl, isopropenyl, butenyl, pentenyl, isoprene, hexenyl, heptenyl, A 2-propinyl group, and the like, and any hydrogen atom in the hydrocarbon group may be substituted with a known substituent (later) capable of being substituted with a hydrocarbon group. Of these, from the viewpoint of semiconductor characteristics, the number of carbon atoms is preferably 25 or less, more preferably 22 or less.

Specific examples of a known capable substituted with an acyclic hydrocarbon group of 1 to 30 carbon atoms wherein the substituent, -F, -Cl, -Br, an alkoxy group, a thioalkoxy group, an amino group, -SO ₂ NHY ¹ (Y ¹ is a substituent -COOY ² (Y ² represents an alkyl group which may have a substituent), -N ₃ , -CN, -NC, -NO ₂ , -NY ³ ₃ ⁺ A ^- (Y ³ represents hydrogen Or an alkyl group which may have a substituent and A ^- represents a monovalent anionic species), -OH, -O ^- L ⁺ (L ⁺ represents a monovalent cation species such as Li ⁺ , Na ⁺ , K ⁺ represents ^{a), -SH, -S - L +} (L + ^{is, Li +, Na +, K} +, a monovalent cation species, such as an ammonium _{salt), -SO 2 H, -SO 2} - L + (L is ^+, Li ^+, Na ^+, K ^+, a monovalent cation species, such as an ammonium _{salt), -SO 3 H, -SO 3} - L + (L + is, Li ^+, Na ^+, K ^+, ammonium salt, etc. -CHO, -COOH, -COO ^- L ⁺ (L ⁺ represents Li ⁺ , Na ⁺ , K ⁺ , ammonium salts, and the like) (Y ⁴ represents hydrogen or an alkyl group which may have a substituent), -SiY ⁵ ₃ (Y ⁵ represents hydrogen or an alkyl group which may have a substituent), -B (OY ⁴ ) _{3 ^{, -Si (OY 6) 3 (}} Y 6 represents an alkyl group which may have a hydrogen atom or a substituent group), -P (= O) ( OY 7) 2 (Y 7 represents an alkyl group which may have a hydrogen atom or a substituent group) , -CONY ⁹ Y ¹⁰ (Y ⁹ and Y ¹⁰ each independently represent hydrogen or an alkyl group which may have a substituent), and preferably -F, -Cl, an amino group, a hydroxyl group, -P _{(= O) (OH) 2} , -SO 2 NHY 1 (Y 1 represents an alkyl group which may have a substituent), an alkoxy group.

Examples of the cyclic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent include a cyclopentyl group, a cyclohexyl group, a phenyl group, a naphthyl group and the like, and any known hydrogen atoms in the cyclic hydrocarbon group may be substituted with a cyclic hydrocarbon group May be substituted with a substituent (latter group).

Specific examples of the known substituent which can be substituted with the cyclic hydrocarbon group include -F, -Cl, -Br, an alkoxy group, a thioalkoxy group, an amino group, -SO ₂ NHY ¹ (Y ¹ represents an alkyl group which may have a substituent) , -COOY ² (Y ² represents an alkyl group which may have a substituent), -N ₃ , -CN, -NC, -NO ₂ , -NY ³ ₃ ⁺ A ^- (wherein Y ³ represents hydrogen or a represents an alkyl group, a ^- is a monovalent anion ^{species), -OH, -O - L +} (L + ^{is, Li +, Na +, K} +, a monovalent cation species, such as an ammonium salt), -SH , -S ^- L ⁺ (L ^{+ is, Li +, Na +, K} +, a monovalent cation species, such as an ammonium _{salt), -SO 2 H, -SO 2} - L + (L + is, Li ^+, Na ^+, K ^+, a monovalent cation species, such as an ammonium _{salt), -SO 3 H, -SO 3} - L + (L + is, Li ^+, Na ^+, a monovalent cation species, such as K ^+, ammonium salt ^{shows), -CHO, -COOH, -COO -} L + (L + is, Li ^+, Na ^+, 1-valent cationic species, such as K ^+, ammonium salt _{^{Shows), -B (OY 4) 3}} (Y 4 represents an alkyl group which may have a hydrogen atom or a substituent group), -SiY ⁵ ₃ (Y ⁵ represents an alkyl group which may have a hydrogen or a substituent), -Si (OY ⁶ ) ₃ (wherein Y ⁶ represents hydrogen or an alkyl group which may have a substituent), -P (= O) (OY ⁷ ) ₂ (Y ⁷ represents hydrogen or an alkyl group which may have a substituent), -CONY ⁹ Y ¹⁰ (Y ^9, Y ¹⁰ represents an alkyl group which may have a hydrogen or a substituent, each independently), an alkyl group, an aryl group, a heteroaryl group, -N = NY ⁸ (Y ⁸ is an alkyl group or a substituent which may have a substituent a represents an aryl group which may have) and the like, preferably, -F, -Cl, -CN, amino group, hydroxyl group, -P (= O) (OH ) 2, -SO 2 NHY 1 (Y 1 Represents an alkyl group which may have a substituent), an alkoxy group, an alkyl group or an aryl group.

Examples of the heteroaryl group which may have a substituent include pyrrolyl, thienyl (2-thienyl, 3-thienyl), pyrazolyl, thiazolyl, benzothiazolyl, , And a benzotriazolyl group. Examples of the substituent include a known substituent (latter group) that can be substituted with a heteroaryl group.

Specific examples of the commonly known substituents which can be substituted with the heteroaryl group include -F, -Cl, -Br, an alkoxy group, a thioalkoxy group, an amino group, -SO ₂ NHY ¹ (Y ¹ represents an alkyl group which may have a substituent -COOY ² wherein Y ² represents an alkyl group which may have a substituent, -N ₃ , -CN, -NC, -NO ₂ , -NY ³ ₃ ⁺ A ^- (wherein Y ³ represents hydrogen or a substituent represents an alkyl group, a ^- is a monovalent anion species), -OH, ^{-O-L +} (L ⁺ is, Li ^+, Na ^+, K ^+, a monovalent cationic species such as ammonium salts), - ^{SH, -S - L + (L} + is, Li ^+, Na ^+, K ^+, a monovalent cation species, such as an ammonium _{salt), -SO 2 H, -SO 2} - L + (L + is, Li ⁺ , Na ⁺ , K ⁺ , and ammonium salts), -SO ₃ H, -SO ₃ ^- L ⁺ (L ⁺ represents a monovalent cation species such as Li ⁺ , Na ⁺ , K ⁺ represents ^{a), -CHO, -COOH, -COO -} L + (L + ^{is, Li +, Na +, K} +, 1 -valent cations such as ammonium salt It represents _{^{a), -B (OY 4) 3}} (Y 4 represents an alkyl group which may have a hydrogen atom or a substituent group), -SiY ⁵ ₃ (Y ⁵ represents an alkyl group which may have a hydrogen or a substituent), -Si ( OY ⁶ ) _{3 wherein} Y ⁶ represents hydrogen or an alkyl group which may have a substituent, -P (= O) (OY ⁷ ) ₂ (Y ⁷ represents hydrogen or an alkyl group which may have a substituent), -CONY ⁹ Y ¹⁰ (Y ^9, Y ¹⁰ are each independently, an alkyl group which may have a hydrogen atom or a substituent group), an alkyl group, an aryl group, a heteroaryl group, -N = NY ⁸ (Y ⁸ is an alkyl group which may have a substituent or an aryl group which may have a substituent) and the like, preferably, -F, -Cl, -CN, amino group, hydroxyl group, -P (= O) (OH ) 2, -SO 2 NHY 1 (Y ¹ represents an alkyl group which may have a substituent), an alkoxy group, an alkyl group or an aryl group.

The phthalocyanine having a substituent represented by the general formula (3) or (4) is a compound in which at least one hydrogen of the phthalocyanine skeleton is substituted with a sulfamoyl group (-SO ₂ NZZ ') (sulfamoyl group substituted phthalocyanine). A, b, c, and d in the general formula (3) or (4) represent the number of introduced substituent groups of the sulfamoyl group and independently represent an integer of 0 to 4, but at least one thereof is not zero. That is, the number of the sulfamoyl groups introduced is at least one, preferably at most four, more preferably at most two, and most preferably at most one. The substitution position is not particularly limited.

Formula (3) or a substituent of a phthalocyanine having a substituent represented by the formula (4) (a sulfamoyl group: -SO ₂ NZZ ') Specific examples below, the substituents used in the nano-sized phthalocyanine structure of the present invention Is not limited to these.

-SO ₂ NH-CH ₃

-SO ₂ NH-CH ₂ CH ₃

_{-SO 2 NH-CH 2 CH 2} CH 3

_{-SO 2 NH-CH (CH 3} ) 2

-SO ₂ NH-CH ₂ CH ₂ CH ₂ CH ₃

_{-SO 2 NH-CH (CH 3} ) (CH 2 CH 3)

_{-SO 2 NH-CH 2 -CH (} CH 3) 2

_{-SO 2 NH-C (CH 3} ) 3

_{-SO 2 NH- (CH 2) 4} CH 3

_{-SO 2 NH- (CH 2) 5} CH 3

_{-SO 2 NH- (CH 2) 7} CH 3

_{-SO 2 NH- (CH 2) 11} CH 3

_{-SO 2 NH- (CH 2) 17} CH 3

_{-SO 2 NH- (CH 2) 21} CH 3

-SO ₂ NH-Cy

(Cy represents a cyclohexyl group)

-SO ₂ NH-Ph

-SO ₂ NH-Th

(Th represents thienyl group)

-SO ₂ N (CH _{3) 2}

-SO ₂ N (CH ₂ CH ₂ CH ₃ ) ₂

The phthalocyanine having a substituent represented by the general formula (3) or (4) can be obtained by combining known publicly known methods. For example, copper phthalocyanine sulfonyl chloride may be reacted with an amine represented by the following formula [10].

[10]

Copper phthalocyanine sulfonyl chloride as a raw material can be obtained by the reaction of copper phthalocyanine with chlorosulfonic acid or thionyl chloride. The amine represented by the formula [10] as the other raw material can be obtained by a known method. For example, it can be obtained by reductive amination of a hydroxyl group of an alcohol using a nickel / copper / chromium catalyst, and the hydroxyl group is converted into a hydroxyl group by a Mitsunobu reaction (reference: Synthesis 1981 , P.1), followed by amination by hydrazine reduction (References: Chemical Communications, 2003, P.2062). In addition, many amines are also available as commercial products.

<Production method of phthalocyanine nano-sized structure>

As a method of producing the phthalocyanine nano-sized structure of the present invention, for example, the methods described in WO2010 / 122921, Nos. 2009-280531 and WO2011 / 065133 can be used. The method of reducing the aspect ratio of the nano-sized structure by adjusting the long-diameter / short-width ratio (aspect ratio) of the nano-sized structure obtained by the method described in these publications is also the same as that of the phthalocyanine nano- Can be used in the production method. Specific examples are shown below.

One example of the method for producing the phthalocyanine nano-sized structure of the present invention is a method for producing a nano-

(a) a step of dissolving said unsubstituted phthalocyanine and said substituent-containing phthalocyanine in a good solvent (good solvent) and then precipitating in a poor solvent (poor solvent) to obtain a complex;

(b) a step (b) of forming the composite into fine particles to obtain an atomized composite, and

(c) a step (c) of forming the nano-sized one-dimensional structure (nanowire or nanorod) by one-dimensional crystal growth (crystal growth in one direction)

.

(Step (a))

In general, it is known that phthalocyanines are soluble in acid solvents such as sulfuric acid. In the method for producing the phthalocyanine nano-sized structures of the present invention, first, the phthalocyanine (sulfamoyl group substituted phthalocyanine) having the above- , Chlorosulfuric acid, methanesulfonic acid, trifluoroacetic acid and the like. Thereafter, the mixture is poured into a poor solvent such as water to precipitate the complex of the unsubstituted phthalocyanine and the phthalocyanine having the substituent.

Here, the mixing ratio of the phthalocyanine (sulfamoyl group-substituted phthalocyanine) having the substituent to the unsubstituted phthalocyanine is preferably in the range of 1 to 200 mass%, more preferably 1 to 120 mass%. When the mixing ratio is 1% by mass or more, it is favorably crystallized in one direction through a process described later by the action of the substituent of the phthalocyanine having the substituent to be favorably a one-dimensional structure, while if it is in the range of 200% Since the functional group is not so large as to inhibit crystal growth, it is preferably a one-dimensional structure through one-directional crystal growth and does not become an amorphous state or an isotropic structure.

The amount of the unsubstituted phthalocyanine to be added to the acid solvent of the substituted phthalocyanine is not particularly limited as long as it is free of unheated components and can be completely dissolved. However, the range of maintaining the viscosity to such an extent that the solution has sufficient fluidity , Preferably 20 mass% or less.

When a solution of the unsubstituted phthalocyanine and the phthalocyanine having the substituent is dissolved in a poor solvent such as water to precipitate a complex of the unsubstituted phthalocyanine with the phthalocyanine having the substituent, By mass to 50% by mass. When the concentration is 0.01 mass% or more, the concentration of the complex to be precipitated is sufficiently high, so that the solid content can be easily recovered. When the content is 50 mass% or less, all the unsubstituted phthalocyanine and the phthalocyanine having the substituent are precipitated to form a solid- There is no component, and recovery is easy.

The poor solvent is not particularly limited as long as the unsubstituted phthalocyanine and the substituent-containing phthalocyanine are insoluble or poorly soluble. However, the homogeneity of the precipitated complex can be maintained at a high level, Water or an aqueous solution containing water as a main component is the most preferable poor solvent.

The complex is filtered using a filter paper and a Buchner funnel to remove the acidic water and washed with water until the filtrate becomes neutral to recover the hydrolyzed complex. The recovered composite may be dehydrated and dried to remove water, or may be left in a functional state in the case of making fine particles by a wet process using a dispersion solvent having affinity for water in the next step (b).

The composite of the unsubstituted phthalocyanine and the phthalocyanine having a substituent obtained in the present step (a) was confirmed to be a structure having an isotropic shape without a crystal grain boundary, as a result of observation by a transmission electron microscope.

(Step (b))

The step (b) is not particularly limited as long as the composite obtained through the step (a) can be made into fine particles. Although there are a dry method and a wet method (a method of carrying out microparticulation in a dispersion solvent), there is a method of making the composite into fine particles. In consideration of the one-dimensional nano-sized structure by carrying out crystal growth in one direction in the solvent in the step (c) , It is preferable that the composite is made into fine particles by a wet process.

Examples of the wet method include a method in which the complex obtained in the step (a) is treated with a dispersing solvent and a media dispersing machine using fine beads such as a bead mill and a paint conditioner, and an emulsifying dispersing machine typified by a TK fill mix manufactured by Freimix And a method of using a jet mill represented by a nanometer of Yoshida Kikai Co., Ltd., and the like. In addition, by using an ultrasonic homogenizer, treatment by ultrasonic irradiation with high power can also be adapted, and these methods can be performed by one or a plurality of methods.

Examples of the dispersion solvent used in the wet method include water, an organic solvent, and a hydrous organic solvent. Examples of the organic solvent include alcohols such as ethanol and the like, glycols and glycol esters in addition to the organic solvent (latter stage) to be used in the step (c) described later, and one or more kinds of these dispersion solvents may be used But is preferably water, ethanol, methanol, chlorobenzene, dichlorobenzene, N-methyl-2-pyrrolidone or propylene glycol monomethyl ether acetate in view of crystal growth and inhibition of crystal transition.

There is no particular limitation on the mass ratio of the complex to the dispersion solvent in carrying out the atomization by the wet process, but from the viewpoint of dispersion efficiency, it is preferable to treat the solid concentration in the range of 1 to 30 mass%. In the case of using micro media such as zirconia beads for the treatment, the bead diameter is preferably in the range of 0.01 to 2 mm in consideration of the degree of dispersion of the composite. The amount of the micro media to be used is most preferably in the range of 100 to 1000 mass% with respect to the dispersion of the composite in terms of the efficiency of fine particle formation and the recovery efficiency.

In addition, in the case of carrying out microparticulation in water, it is preferable to remove water by dehydrating and drying the obtained aqueous dispersion of the microparticulated composite. The method of dewatering and drying is not particularly limited, but may include evaporation by filtration, centrifugation, rotary evaporator and the like. After dewatering, it may be dried by using a vacuum dryer or the like until the water is completely removed.

In the present step (b), it is preferable that the degree of microparticulation is such that the composite obtained in the step (a) has a particle diameter of less than 1 m, and in the step (c) described below, Is preferably less than 500 nm, more preferably less than 300 nm (particle diameter is in accordance with dynamic light scattering), from the viewpoint of promoting the formation of a one-dimensional structure at the nano-size.

(Step (c))

The step (c) is a step of making the nano-sized one-dimensional structure by causing the fine particle hybrid composite obtained through the step (b) to undergo crystal growth (one-dimensional crystal growth) in one direction. The degree of nano-sized one-dimensional structure is preferably such that the shape of the resulting nano-sized one-dimensional structure has a width (short diameter) of 500 nm or less, more preferably 300 nm or less, and most preferably 100 nm or less. The method of forming the nano-sized one-dimensional structure is not particularly limited as far as the nano-sized one-dimensional structure of the nano-sized composite can be obtained. However, the method is not limited to the one in which the nano- And a method of making a structure. Specifically, the composite can be converted into a nano-sized one-dimensional structure by stirring or standing the particulate composite in an organic solvent (in a liquid phase). In stirring or standing, it is preferable that the stirring is performed in a controlled state at a predetermined temperature from the viewpoint of controlling the shape of the nano-sized one-dimensional structure.

When the microparticle-forming complex is converted into a nano-sized one-dimensional structure in an organic solvent (in a liquid phase), the solvent to be used is not particularly limited so long as it has low affinity with the phthalocyanine species. An amide organic solvent having high affinity, an aromatic organic solvent, a halogen organic solvent, a glycol ester solvent, a glycol ether solvent and the like are preferable. Specifically,

As the amide solvent, there are N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone,

As the aromatic organic solvent, toluene, xylene, ethylbenzene,

As the halogen-based organic solvent, chlorobenzene, dichlorobenzene, chloroform, methylene chloride, dichloroethane,

Examples of the glycol ester solvent include ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate,

Examples of the glycol ether solvent include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , Propylene glycol tert-butyl ether and dipropylene glycol monomethyl ether are the most favorable organic solvents. The organic solvent may be used alone, or may be mixed at an arbitrary ratio, or may be used in combination with other organic solvents.

With respect to the amount of the organic solvent added to the particulate composite, it is preferable that the solid content concentration of the complex in the organic solvent is in the range of 0.1 to 20% from the viewpoint of preventing the aggregation, More preferably 1 to 10%.

When the complex is converted into a one-dimensional nano-sized structure, the temperature during stirring or standing is preferably in the range of 5 to 300 캜, more preferably 20 to 250 캜. If the temperature is 5 占 폚 or higher, it is possible to sufficiently induce crystal growth of the phthalocyanine species, and it is possible to grow the one-dimensional structure by the intended one-dimensional crystal growth. Aggregation and fusion are hardly observed, and crystal growth in the direction of the short axis (width) does not lead to coarse (isotropic structure).

There is no particular limitation on the agitation time or the settling time for the one-dimensional structure, but it is preferable to stir or stand for at least 10 minutes or so until the length of the nano-sized one-dimensional structure grows to 100 nm or more.

Here, the solvent used in the present step (c) may be different from the solvent used in the wet microparticulation treatment in the step (b). At this time, after the step (b) is carried out, the solvent used for the wet microparticulation treatment is removed, and the thus obtained microparticulated composite is redispersed in the solvent used in the present step (c). The method for removing the solvent used in the step (b) is not particularly limited, and examples thereof include filtration, centrifugation, and evaporation treatment using a rotary evaporator. After that, it may be dried by using a vacuum drier or the like until the solvent content is completely removed. The method of re-dispersing in the solvent used in the step (c) is not particularly limited. However, it is possible to use a known method such as heat treatment, stirring treatment, dispersion stirring treatment, dispersion uniform treatment, ultrasonic wave irradiation treatment, Ultrasonic dispersion treatment, and the like can be carried out by combining one kind or a plurality of kinds.

In this way, a phthalocyanine nano-sized one-dimensional structure obtained by one-dimensional crystal growth of the microparticulated composite obtained in the step (b) can be obtained. On the other hand, it is also possible to reduce the long diameter / short width ratio (aspect ratio) of the thus obtained nano-sized one-dimensional structure to obtain a one-dimensional structure having an appropriate aspect ratio. Specifically, the nano-sized one-dimensional structure obtained by the above-described method is subjected to a treatment such as stirring treatment, dispersion stirring treatment, dispersion uniform treatment, ultrasonic irradiation treatment, ultrasonic stirring treatment, ultrasonic homogenization treatment, ultrasonic dispersion treatment, Are provided for the treatment of one kind or a combination of plural kinds. By these processes, the aspect ratio of the nano-sized one-dimensional structure can be reduced to an appropriate size.

&Lt; Ink composition &

The ink composition of the present invention contains the phthalocyanine nano size structure of the present invention and an organic solvent as essential components. These ink compositions are well-known as precursor materials for forming active portions (semiconductor layers) of electronic devices by a wet process (printing or coating).

The ink composition of the present invention is produced by dispersing the phthalocyanine nano-size one-dimensional structure in an organic solvent. Alternatively, the dispersion of the phthalocyanine nano-sized one-dimensional structure obtained in the step (c) may be used as the ink composition of the present invention.

The kind of the organic solvent is not particularly limited as far as it can stably disperse the phthalocyanine nano-sized one-dimensional structure. It may be an organic solvent or an organic solvent in which two or more kinds thereof are mixed, There is preferably used, for example, an amide organic solvent, an aromatic organic solvent, a halogen organic solvent, a glycol ester solvent, a glycol ether solvent and the like which have high affinity with phthalocyanines,

As the amide solvent, there are N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone,

As the aromatic organic solvent, toluene, xylene, ethylbenzene,

As the halogen-based organic solvent, chlorobenzene, dichlorobenzene, chloroform, methylene chloride, dichloroethane,

Examples of the glycol ester solvent include ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate,

Examples of the glycol ether solvent include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , Propylene glycol tert-butyl ether and dipropylene glycol monomethyl ether are the most favorable organic solvents for dispersion.

In the ink composition of the present invention, in order to impart a wet process (printing or coating) suitability and film-forming property (film quality after printing or coating), the content of the phthalocyanine nano-size one- , More preferably from 0.1 to 10% by mass.

The ink composition of the present invention may contain other electron-donating materials or hole-transporting materials in addition to the phthalocyanine nano-size one-dimensional structure. As such a material, for example, a? -Conjugated polymer showing semiconductor properties, a? -Conjugated polymer showing semiconductor properties, a low molecular weight organic semiconductor compound and the like can be given. Here, examples of the? -Conjugate polymer showing semiconducting properties include polythiophene, poly (3-hexylthiophene-2,5-diyl) (P3HT), P3HT regio- , Poly-p-phenylenes, polyfluorenes, polypyrroles, polyanilines, polyacetylenes and polythienylenevinylenes. Examples of the non-conjugated polymer showing semiconducting properties include polyvinylcarbazole, Examples of the organic semiconductor compound include soluble or solvent-dispersible phthalocyanine derivatives, soluble or solvent-dispersible porphyrin derivatives, and 6,13-bis (triisopropylsilylethynyl) pentacene (TIPS-pentacene). Among these, polymeric materials have the effect of imparting a wet process (printing or coating) suitability and film-forming property (film quality after printing or coating) to the ink composition as described later.

The ink composition of the present invention may contain an electron-accepting material typified by fullerene. As a result, it is possible to form the active portion (photoelectric conversion layer) by forming the film once in the case of providing the photoelectric conversion element. Examples of the electron-accepting material usable in the present invention include naphthalene derivatives, perylene derivatives, oxazole derivatives, triazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, fullerenes, carbon nanotubes (CN-PPV), Boramer (trade name, manufactured by TDA Research), a CF ₃ group or a F group-introduced low molecular weight organic semiconductor material or a polymer organic material Semiconductor materials and the like. Examples of the naphthalene derivative include 1,4,5,8-naphthalene tetracarboxylic diimide (NTCDI), N, N'-dialkyl-1,4,5,8-naphthalene tetracarboxylic diimide NTCDI-R (alkyl is an alkyl group having from 1 to 18 carbon atoms), 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTCDA), and the like, Perylene tetracarboxylic dianhydride (PTCDA), 3,4,9,10-perylene tetracarboxylic bisbenzimidazole (PTCBI), 3,4,9,10-perylene tetracarboxylic (PTCDI), N, N'-dimethyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C1), N, N'-dipentyl- Perylene tetracarboxylic diimide (PTCDI-C5), N, N'-dioctyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C8) 4,4,9,10-perylene tetracarboxylic diimide (PTCDI-Ph); oxazole derivatives such as 2- (4-biphenylyl) -5- (4-t-butylphenyl) ) -1,3,4-oxadiazole ( (4-biphenylyl) -4-phenyl-5- (4-methoxyphenyl) -1,3,4-oxadiazole (BND) (4-t-butylphenyl) -1,2,4-triazole (TAZ). Examples of the phenanthroline derivatives include basocuproin (BCP) and bazophenanthroline , 6,6] -phenyl C61 butyric acid methyl ester (aka PCBM or [60] PCBM), [6,6] -phenyl C61 PCB-C8 butyric acid butyl ester (aka PCBB), [6,6] -phenyl C61 butyric acid hexyl ester ([6,6] -PCBH), [6,6] -phenyl C61 butyric acid octyl ester 6,6] -phenyl C61 butyrate dodecyl ester ([6,6] -PCBD), [60] ThPCBM, (6,6) -phenyl C71 butyrate methyl ester (aka PC70BM or [ , 6) -phenyl C85 butyric acid methyl ester (also known as PC84BM or [84] PCBM). Among them, fullerene derivatives are preferably used since they have a high charge separation rate and a high electron transfer rate. Of the fullerenes, PCBM and C70 derivatives (PC70BM and the like) are more preferable because of their excellent charge separation speed and electron transfer speed, and higher photoelectric conversion efficiency.

Among the above electron-accepting materials, a polymer material (an electron-accepting polymer) such as a derivative (CN-PPV) into which a poly-p-phenylenevinylene cyanogen group is introduced and Boramer (trade name, a product of TDA Research) (Printing or coating) suitability and film formability (film quality after printing or coating) to the ink composition (or the material for photoelectric conversion elements) in addition to the semiconductor function such as separation and electron transfer Do.

With regard to the mixing ratio of the ink composition of the present invention with the phthalocyanine nano-sized nano-sized one-dimensional structure and the electron-accepting material, the photoelectric conversion element described later can be arbitrarily selected within the range in which the photoelectric conversion property can be obtained, but the phthalocyanine nano- The electron accepting material is preferably in the range of 1/99 to 99/1, more preferably in the range of 1/9 to 9/1, and still more preferably in the range of 2/8 to 8/2.

In the ink composition of the present invention, when an electron-accepting material is added, the content of the total amount of the phthalocyanine nano-sized one-dimensional structure and the total amount of the electron-accepting material is preferably from 0.05 to 20 mass%, more preferably from 0.1 to 10 mass% By mass.

To the ink composition of the present invention, a resin component may be added as a rheology adjustment or a binder component in order to impart a wet process (printing or coating) suitability and film-forming property (film quality after printing or coating). The resin is not particularly limited as long as it is a known resin, and may be used alone or in combination of two or more resins, but polymethyl methacrylate, polystyrene, polycarbonate and the like are preferable.

If the content of these resins is too large, the viscosity excessively increases, which affects the film-forming property by printing or coating, and polymethyl methacrylate, polystyrene, polycarbonate, etc. are electrically inactive, The concentration of the phthalocyanine nano-sized structure of the present invention is relatively reduced, so that the semiconductor characteristics exhibited by the phthalocyanine nano-sized structure of the present invention are reduced. Therefore, the content of the resin in the ink composition is preferably 20% by mass or less, more preferably 10% by mass or less.

In the ink composition of the present invention, sieving components, various surfactants, and the like can be added as needed for the main purpose of improving the wet process (printing or coating) aptitude and film formability (film quality after printing or coating).

As the sieving component, there may be used a known fine particle powder for a known purpose and a dispersion in which these fine particle powders are dispersed in advance in a dispersing agent or an organic solvent, so long as they can maintain the semiconductor characteristics, and they may be used singly or in combination none. Specific examples thereof include a silicone oil such as Aerosil series (trade name, Ebonic), Silicia, Silo Fobic, Silopus, Silo page, Silo Pure, Cyrospear, Silo mask, Silwell, Fuji balloon PMA-ST, IPA-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.), NANOBIC3600 series, NANOBIC3800 series (above, trade name, manufactured by Big Chemie), and the like. These may be used alone or in combination of two or more. Further, since the photoelectric conversion element transports the charge in the film thickness direction, the surface smoothness of the film is required. For this reason, the average particle size of the sieving components to be added to the ink is preferably 1 to 150 nm, more preferably 5 to 50 nm, more preferably PMA-ST, IPA-ST (trade name, available from Nissan Chemical Industries, ), And NANOBIC3600 series (trade name, manufactured by Big Chemie). The average particle diameter can be easily measured by, for example, a dynamic light scattering method. In addition, since these constituents are electrically inactive, if the content is too high, the concentration of the phthalocyanine nano size structure of the present invention becomes relatively thin, so that semiconductor characteristics expressed by the phthalocyanine nano size structure of the present invention are reduced. Therefore, the sieving component content in the ink composition is 90% by mass or less, preferably 70% by mass or less, of the total solid content.

Examples of the surfactant include hydrocarbon-based, silicone-based, and fluorine-based surfactants, and these surfactants may be used alone or in combination of two or more. Among them, the preferred fluorine-based surfactant is a nonionic fluorine-based surfactant having a straight chain perfluoroalkyl group and a chain length of C6 or more, more preferably C8 or more. Specific examples thereof include Megapack F-482, Megapack F-470 (R-08), Megapack F-472SF, Megapack R-30, Megapack F-484, Megapack F- F-172D, Megafac F178RM (trade name, manufactured by DIC), and the like. These may be used alone or in combination of two or more. These surfactants are contained in the ink composition in an amount of 5.0% by mass or less based on the active ingredient, preferably 1.0% by mass or less based on the active ingredient.

In the ink composition of the present invention, the materials described above are mixed and used. The mixing method is not particularly limited, but the material of the base material may be added to the solvent at a desired ratio, and then the mixture may be subjected to known methods such as heat treatment, stirring treatment, dispersion stirring treatment, dispersion equalization treatment, Stirring method, ultrasonic homogenization, ultrasonic dispersion treatment, laser irradiation treatment, and the like may be combined and dispersed in a solvent.

<Electronic device>

Next, the electronic device of the present invention will be described. The electronic device of the present invention is an electronic device containing the phthalocyanine nano-sized one-dimensional structure of the present invention in the active layer portion (semiconductor layer). Specific examples of the electronic device include a photoelectric conversion element such as a solar cell or a light receiving element, a transistor such as a field effect transistor, an electrostatic induction transistor or a bipolar transistor, an electroluminescent element, a temperature sensor, a gas sensor, a humidity sensor, But the present invention is not limited thereto.

<Photoelectric Conversion Element>

Next, the photoelectric conversion element of the present invention will be described. The photoelectric conversion element of the present invention has at least one pair of electrodes, that is, an anode and a cathode, and includes the phthalocyanine nano-sized structure of the present invention between these electrodes. 1 is a schematic diagram showing an example of a photoelectric conversion element of the present invention. In Fig. 1, reference numeral 1 denotes a substrate, reference numeral 2 denotes an electrode a, reference numeral 3 denotes a photoelectric conversion layer (organic semiconductor layer) including the phthalocyanine nano size structure of the present invention, and reference numeral 4 denotes an electrode b.

The organic semiconductor layer 3 is a film containing the phthalocyanine nano-sized one-dimensional structure of the present invention. Further, the organic semiconductor layer 3 is a film formed of the ink composition of the present invention.

When the organic semiconductor layer 3 contains an electron-accepting material, the phthalocyanine nano-size structure of the present invention and the electron-accepting material may be mixed or laminated. Fig. 2 shows an example of the case of stacking. It is preferable that the layer having the phthalocyanine nano-sized structure of the present invention as the electron-accepting material is on the anode side and the layer having the electron-accepting material is on the cathode side. Therefore, in the case where the layer 5 having the phthalocyanine nano-sized one-dimensional structure of the present invention and the layer 6 containing the electron-accepting material are shown in Fig. 2, the electrode a of the numeral 2 is the anode and the electrode b of the numeral 4 is the cathode do. In addition, in the case of the laminated structure, "other electron-donating material other than the above-described phthalocyanine nano-sized one-dimensional structure" may be contained in the layer (code 5) containing the phthalocyanine nano- (6) containing an electron-accepting material.

The thickness of the organic semiconductor layer (3 in Fig. 1, 5 and 6 in Fig. 2) is a thickness capable of sufficiently absorbing light and is not particularly limited as long as it does not cause deactivation of charge. More preferably 10 to 500 nm, and more preferably 20 to 300 nm. When laminated, the layer having the phthalocyanine nano-sized structure of the present invention preferably has a thickness of 1 to 500 nm, more preferably 5 to 300 nm, of the thickness.

The organic semiconductor layer can be obtained by forming the ink composition of the present invention by a wet process (printing or coating) and drying it. The method of forming the ink composition of the present invention is not particularly limited and a publicly known method can be employed. Specifically, the ink-jet method, the gravure printing method, the gravure offset printing method, the offset printing method, the relief printing method, A roll coater method, a squeeze coater method, an impregnation coater method, a transfer roll coater method, a kiss coater method, an air knife coater method, an air knife coater method, A cast coater method, a spray coater method, an electrostatic coater method, an ultrasonic spray coater method, a die coater method, a spin coater method, a bar coater method, a slit coater method and a drop cast method.

When the organic semiconductor layer is laminated as shown in Fig. 2, the ink composition of the present invention including the phthalocyanine nano-size one-dimensional structure is formed by the above-described method, and then the electron- . &Lt; / RTI &gt; It is to be noted that since the phthalocyanine nano-size structure of the present invention has a high solvent resistance after film formation, it is possible to laminate an electron-accepting material with a wet process.

As the substrate 1, silicon, glass, various resin materials, and the like can be used. Examples of the various resin materials include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylenesulfide, polyarylate, polyimide , Polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), and acrylic resin. By using such a resinous material, the weight can be reduced as compared with the case where glass is used, the portability can be increased, and the resistance to impact can be improved.

On the other hand, when light is incident from the substrate side, a material having good light transmittance is preferable. Examples of such materials include glass, PET, PC, polyimide, PES and acrylic resin.

As the material for the electrodes a and b, it is preferable to use a conductive material having a large work function for one of the electrodes and a conductive material having a small work function for the other electrode. An electrode using a conductive material having a large work function becomes an anode. In addition to metals such as gold, platinum, chromium and nickel, metal oxides such as indium and tin, complex metal oxides (indium tin oxide (ITO), indium zinc oxide (IZO) A conductive polyaniline, a conductive polypyrrole, a conductive polythiophene, and a polyethylene dioxythiophene (hereinafter, referred to as &quot; conductive polyaniline &quot; PEDOT)) is preferably used. Here, it is preferable that the conductive material used for the anode is ohmic-bonded to the organic semiconductor layer 3. In the case of using the buffer layer 1 to be described later, it is preferable that the conductive material used for the anode is ohmic-bonded to the buffer layer 1.

An electrode using a conductive material having a small work function becomes a cathode. As the conductive material having a small work function, an alkali metal or an alkaline earth metal, specifically, lithium, magnesium, calcium or the like is used. Further, tin, silver, aluminum and the like are also preferably used. Further, an electrode comprising an alloy made of the above metal or a laminate of the above metals is also preferably used. Here, the conductive material used for the cathode is preferably ohmic-bonded to the organic semiconductor layer 3. In the case of using the buffer layer 2 to be described later, it is preferable that the conductive material used for the cathode is ohmic-bonded to the buffer layer 2.

In the photoelectric conversion element of the present invention, it is preferable that either the electrode a or the electrode b has light transmittance. The light transmittance of the electrode is not particularly limited as long as the incident light reaches the organic semiconductor layer 3 to generate an electromotive force. As such a conductive material, for example, it is possible to improve the conductivity by doping ITO (indium oxide-tin oxide composite), FTO (fluorine-doped tin oxide), (laminated) graphene, (Conductive polyaniline, conductive polypyrrole, conductive polythiophene, polyethylenedioxythiophene (PEDOT), etc.) commonly used in the present invention are suitably used. These materials may also be used in combination with a metal material having a high conductivity, in the form of a mesh.

The thickness of the electrode is not particularly limited as long as it has optical transparency and conductivity, and it is preferably from 5 to 10,000 nm, more preferably from 10 to 5,000 nm, and still more preferably from 20 to 300 nm, depending on the electrode material. When the other electrode is conductive, light transmittance is not necessarily required, and the thickness is not particularly limited.

The electrode may be formed by a dry process such as a vacuum evaporation method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method or an atmospheric pressure plasma method, , A gravure printing method, a gravure offset printing method, an offset printing method, a convex printing method, a convex printing method, a screen printing method, a microcontact printing method, a reverse coater method, an air doctor coater method, a blade coater method, A roll coater method, a squeeze coater method, an impregnation coater method, a transfer roll coater method, a kiss coater method, a cast coater method, a spray coater method, an electrostatic coater method, an ultrasonic spray coater method, a die coater method, A slit coater method, and a wet casting method of a drop casting method, and can be appropriately used depending on the material. More specifically, a conductive solid film formed by a dry process such as vapor deposition or sputtering, a method of forming an electrode through a pattern mask or the like by using a dry process such as vapor deposition or sputtering, or the like by photolithography- A method of forming an electrode, a method of forming an electrode by a combination of a dry process such as vapor deposition or sputtering and a photolithography method and a lift-off method, a method of forming a conductive solid film using a dry process such as vapor deposition or sputtering, And a method of etching by use. The conductive fine particle dispersion or the conductive polymer solution or dispersion may be directly patterned by a wet process such as an inkjet method, a screen printing method, a gravure offset printing method, a convex plate reverse printing method, a micro contact printing method, etc., After the film is formed, it may be patterned by a photolithography-etching method or a laser ablation method for publicly known techniques, or may be patterned by a combination of a wet process and a photolithographic method and a lift-off method.

In the photoelectric conversion element of the present invention, the buffer layer 1 may be provided between the anode and the organic semiconductor layer. The buffer layer 1 is used as needed in order to enable efficient extraction of charges. Examples of the material for forming the buffer layer 1 include oxides such as oxide graphene, modified graphene, polythiophenes, polyanilines, poly-p-phenylenevinylene, polyfluorenes, polyvinylcarbazoles, phthalocyanine derivatives (H2Pc , CuPc, ZnPc, etc.), porphyrin derivatives and the like are preferably used. These materials may be those having increased conductivity (hole transportability) by doping. In particular, polyethylene dioxythiophene (PEDOT), which is a polythiophene, and PEDOT: PSS, which is doped with PEDOT and polystyrene sulfonate (PSS), are preferably used. The thickness of the buffer layer 1 is preferably 5 to 600 nm, more preferably 10 to 200 nm.

In the photoelectric conversion element of the present invention, the buffer layer 2 may be provided between the organic semiconductor layer and the cathode. The buffer layer 2 is used as needed in order to enable efficient extraction of charges. (Naphthalene derivatives, perylene derivatives, oxazole derivatives, triazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, fullerenes and carbon nanotubes (CNT)) as the material for forming the buffer layer 2, (CN-PPV), Boramer (trade name, manufactured by TDA Research), a CF ₃ group or a F group-introduced low molecular weight organic semiconductor Materials or polymeric organic semiconductor materials), it is possible to use perfluoro compounds such as octaazoporphyrin, perfluoropentacene and perfluorophthalocyanine, electron-donating compounds such as tetrathiopolvalene and tetramethylphenylenediamine, A charge transfer complex composed of an electron-accepting compound such as ananoquinodimethane or tetracyanoethylene, an n-type inorganic oxide such as titanium oxide, zinc oxide, or gallium oxide, , And the like may be used an alkali metal compound such as lithium fluoride, sodium fluoride, cesium fluoride. The thickness of the buffer layer 2 is preferably 0.5 to 600 nm, more preferably 1 to 200 nm.

Examples of the method for forming the buffer layer include a dry process such as a vacuum evaporation method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method, an ink jet method, a gravure printing method, A roll coater method, a squeeze coater method, an offset printing method, an offset printing method, a convex printing method, a convex inversion printing method, a screen printing method, a microcontact printing method, a reverse coater method, an air doctor coater method, A roll coater method, a cast coater method, a spray coater method, an electrostatic coater method, an ultrasonic spray coater method, a die coater method, a spin coater method, a bar coater method, a slit coater method, Wet process, and can be used depending on the material.

In the case of using an inorganic oxide as the buffer layer, a method in which fine particles of inorganic oxide are dispersed in an optional organic solvent or water, using a dispersion auxiliary such as a surfactant, is applied and dried, , A so-called sol-gel method in which a solution of an oxide precursor, for example, an alkoxide, is applied and dried can be used.

These buffer layers may be a single layer or may be formed by stacking other materials.

The photoelectric conversion element according to the present invention can constitute a solar cell module by integration. At this time, the photoelectric conversion element of the present invention may be structured such that the above-described photoelectric conversion element is shielded from the external air including moisture by a protective sheet or an adhesive sealing material. As the solar cell module, by bringing the electrode a of the photoelectric conversion element according to the present invention into contact with the electrode b of the photoelectric conversion element according to another aspect of the present invention, the photoelectric conversion element according to the present invention is connected in series and integrated And the like.

Further, the electrodes a of the adjacent photoelectric conversion elements according to the present invention are brought into contact with each other, and the electrodes b of the adjacent photoelectric conversion elements according to the present invention are brought into contact with each other, whereby the photoelectric conversion elements according to the present invention are connected in parallel And then integrating the solar cell module.

(transistor)

Next, the transistor of the present invention will be described. The transistor of the present invention is a transistor containing the phthalocyanine nano-size structure of the present invention in an active portion (in a transistor, referred to as a channel portion (semiconductor layer)).

Examples of such a transistor include a top gate type in which a film including a phthalocyanine nano-sized structure according to the present invention, a source electrode and a drain electrode connected to the film, and a gate electrode are formed thereon via a gate insulating film, have.

Alternatively, a bottom gate type in which a film including a phthalocyanine nano-sized structure according to the present invention and a source electrode and a drain electrode connected to the film are formed via a gate insulating film by forming a priority gate electrode on a substrate may also be used.

Fig. 3 is a schematic diagram showing a transistor having a film 12 containing a phthalocyanine nano-sized structure according to the present invention and formed of a bottom gate bottom contact type. Here, the thickness of the film 12 containing the phthalocyanine nano-size structure of the present invention can be set to an arbitrary value, for example, 50 to 10000 nm.

As the substrate 7, silicon, glass, flexible resin sheet (plastic film), or the like is used. Examples of the plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylenesulfide, polyarylate, polyimide, And films made of polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like. As described above, by using the plastic film, the weight can be reduced as compared with the case of using the glass substrate, the reflection can be increased, and the resistance to impact can be improved.

The material for forming the source electrode 10, the drain electrode 11 and the gate electrode 8 is not particularly limited as long as it is a conductive material and may be a metal such as platinum, gold, silver, nickel, chromium, copper, iron, tin, , Indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide, antimony, indium tin oxide (ITO), fluorine doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste, lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium-potassium alloy, magnesium / copper mixture, Gold, silver, copper, aluminum, indium, ITO, and carbon are preferable, although a lithium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide mixture, and a lithium / aluminum mixture can be used. Further, conventionally known conductive polymers improving conductivity by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, complexes of polyethylene dioxythiophene and polystyrenesulfonic acid are also suitably used. Of these, gold, silver, platinum, copper, a conductive polymer, and ITO, which have a low electrical resistance at the interface with the semiconductor layer, are preferable.

As a method of forming the electrode, a method similar to that of the electrode of the photoelectric conversion element can be used.

As the gate insulating layer 9, various insulating films can be used. In consideration of cost merit, it is preferable to use a polymer-based organic material, and in order to obtain high properties, use of an inorganic oxide having a high dielectric constant is preferable. Examples of the polymer organic material include polyimide, polyamide, polyester, polyacrylate, photo radical polymerization type, photocurable resin of photocationic polymerization type, copolymer containing acrylonitrile component, polyvinyl phenol, polyvinyl Alcohol, novolak resin, epoxy resin, and cyanoethylpullulan can be used. Examples of the inorganic oxide include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconium citrate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, barium titanate, barium magnesium fluoride, Bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, and yttrium trioxide. Among them, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

Examples of the method for forming the insulating film include dry processes such as a vacuum evaporation method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method and an atmospheric pressure plasma method; an inkjet method, Such as a gravure offset printing method, an offset printing method, a convex printing method, a convex inversion printing method, a screen printing method, a microcontact printing method, a reverse coater method, an air doctor coater method, an air knife coater method, There can be used various methods such as a coater method, an impregnation coater method, a transfer roll coater method, a kiss coater method, a cast coater method, a spray coater method, an electrostatic coater method, an ultrasonic spray coater method, a die coater method, a spin coater method, Cast method, and the like. When precise patterning is required, an ink jet method, a convex plate reverse printing method, a micro contact Using the wet process, such as a family register, and swaebeop, may, depending on the material used enemy.

In addition, the wet process of the inorganic oxide may be carried out by a method of applying and drying a solution prepared by dispersing fine particles of inorganic oxide in an optional organic solvent or water, using a dispersion auxiliary such as a surfactant if necessary, and a method of applying an oxide precursor, For example, a so-called sol-gel method in which a solution of an alkoxide is applied and dried can be used.

The dried film thickness of these insulating films is 0.1 to 2 占 퐉, preferably 0.3 to 1 占 퐉.

The transistor, which is an electronic element according to the present invention, can constitute an electronic component module by integration. Examples of the electronic component module include a transistor array (see Fig. 4) which is a rear substrate such as a display, an inverter and a ring oscillator which are logic circuits of RFID, and the like.

[Example]

Hereinafter, the present invention will be described more specifically based on examples. The present invention is not limited to the following examples.

(Synthesis Example 1)

50 parts by mass of copper phthalocyanine sulfonic acid (EXT-795 average degree of sulfonation = 0.95, manufactured by DIC Corporation) and 1,000 parts by mass of DMF were cooled to 5 占 폚, and then 50 parts by mass of thionyl chloride was added dropwise. And reacted at 70 ° C for 5 hours. The reaction solution was poured into 5,000 parts by mass of ice water, and the resulting precipitate was recovered and dried to obtain a mixture of copper phthalocyanine sulfonic acid and copper phthalocyanine sulfonyl chloride.

Subsequently, 20 parts by mass of the mixture obtained above was slowly added to a mixture of 23 parts by mass of a 40% aqueous solution of methylmonoamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 20 parts by mass of sodium carbonate and 800 parts by mass of water, . 2,000 parts by mass of THF was added to the reaction solution, and the mixture was filtered through a 5 cm silica gel column, and the filtrate was concentrated. The residue was purified by silica gel column, eluted with chloroform, collected and concentrated to give the compound represented by the following formula [11].

[Figure 11]

(Average substituent introduced number n = 1.1)

(Synthesis Example 2)

In the same manner as in Synthesis Example 1 except that 17.5 parts by mass of n-propyl monoamine (manufactured by TOKYO KASEI K.K.) was used instead of 23 parts by mass of a 40% aqueous solution of methylmonoamine, Was obtained.

[Figure 12]

(Average substituent introduced number n = 1.1)

(Synthesis Example 3)

In the same manner as in Synthesis Example 1 except that 30 parts by mass of hexyl monoamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 23 parts by mass of the 40% aqueous solution of methyl monoamine, &Lt; / RTI &gt;

[Figure 13]

(Average substituent introduced number n = 1.1)

(Synthesis Example 4)

In the same manner as in Synthesis Example 1 except that 55 parts by mass of dodecylmonoamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 23 parts by mass of a 40% aqueous solution of methylmonoamine, To obtain the indicated compound.

[14]

(Average substituent introduced number n = 1.1)

(Synthesis Example 5)

In the same manner as in Synthesis Example 1 except that 80 parts by mass of stearyl monoamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 23 parts by mass of the 40% aqueous solution of methylmonoamine, To obtain the indicated compound.

[Figure 15]

(Average substituent introduced number n = 1.1)

(Synthesis Example 6)

In the same manner as in Synthesis Example 1 except that 29.4 parts by mass of cyclohexyl monoamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 23 parts by mass of a 40% aqueous solution of methyl monoamine, To obtain the indicated compound.

[16]

(Average substituent introduced number n = 1.1)

(Synthesis Example 7)

In the same manner as in Synthesis Example 1 except that 27.6 parts by mass of phenyl monoamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 23 parts by mass of a 40% aqueous solution of methyl monoamine, &Lt; / RTI &gt;

[Figure 17]

(Average substituent introduced number n = 1.1)

(Synthesis Example 8)

The same procedures as in Synthesis Example 1 were carried out except that 29.4 parts by mass of 3-thienyl monoamine was used instead of 23 parts by mass of the 40% aqueous solution of methylmonoamine in Synthesis Example 1 to obtain the compound represented by the following formula [18].

[Figure 18]

(Average substituent introduced number n = 1.1)

(Example 1)

&Lt; Preparation of dispersion of phthalocyanine nano size structure and phthalocyanine nano size structure >

1.6 g of copper phthalocyanine (Fastogen Blue 5380E (trade name, manufactured by DIC)) as an unsubstituted phthalocyanine and 1.2 g of a phthalocyanine derivative represented by the formula [11] obtained in Synthesis Example 1 as a substituent-containing phthalocyanine were dissolved in concentrated sulfuric acid ) To completely dissolve it to prepare a concentrated sulfuric acid solution. Subsequently, 730 g of distilled water was poured into 1000 mL of beaker. After sufficiently cooling with ice water, the concentrated sulfuric acid solution prepared beforehand was added while stirring the distilled water, to obtain a copper phthalocyanine derivative represented by the following formula Was precipitated.

Subsequently, the complex thus obtained was filtered using a filter paper, sufficiently washed with distilled water, and then dehydrated by a vacuum dryer.

12 g of the composite of the above-mentioned unsubstituted copper phthalocyanine and the copper phthalocyanine derivative represented by [Chemical Formula 11] was placed in a polypropylene container having a capacity of 50 mL, and further dichlorobenzene was added thereto to obtain a solution of the complex (solid content) 60 g of zirconia beads having a diameter of 0.5 mm was added to the resulting mixture at a weight ratio of 10% (solid content concentration of 10%), and the mixture was treated with a paint shaker for 2 hours. The dispersion of the microparticulated complex was then separated and recovered from the zirconia beads and further added with dichlorobenzene to reduce the solids concentration to 2% (adjustment of the 2% dispersion of dichlorobenzene in the particulate composite).

Next, 10 g of a 2% dispersion of dichlorobenzene in the above-mentioned particulate composite was put in a pressure-resistant container, and the temperature was raised to 200 DEG C over 90 minutes. After reaching 200 캜, heating was further continued for 30 minutes at the same temperature, and then cooling was carried out. Thus, a phthalocyanine nano-size structure in which phthalocyanine was one-dimensionally crystallized and grown in nano-size was obtained in a state of being dispersed in dichlorobenzene at a solid concentration of 2% (phthalocyanine nano-size structure dispersion (1)).

The phthalocyanine nano size structure was confirmed by observing the shape of the solid content of the dispersion by a transmission electron microscope and observing the crystal structure of the solid film by X-ray diffraction (XRD) measurement. FIG. 5 shows a transmission electron microscope image. From the figure, it was confirmed that the shape of the solid content in the dispersion (1) is a nano-sized structure having a long diameter and a short diameter and a short diameter of 100 nm or less. Further, it was confirmed by XRD measurement that the solid film exhibited peaks at 2? = 6.9, 10.2, and 15.7, and had a crystal structure derived from phthalocyanine? Crystal. From the above, it was confirmed that the solid content obtained by the present production method is a phthalocyanine nano size structure having a long diameter and a short diameter and a short diameter of 100 nm or less.

&Lt; Evaluation of transistor fabrication and transistor characteristics (mobility)

An n-type silicon substrate was prepared and used as a gate electrode, and this surface layer was subjected to thermal oxidation treatment to form a gate insulating film made of silicon oxide. The above-mentioned dispersion (1) of the phthalocyanine nano size structure was spin-coated to form a semiconductor film (channel portion) comprising a phthalocyanine nano size structure. Next, a source / drain electrode made of a gold thin film was pattern-formed by a vapor deposition film to form a transistor 1. [ The channel length L (source electrode-drain electrode interval) was set to 75 μm and the channel width W was set to 5.0 mm.

For the transistor 1, transistor characteristics were evaluated. The transistor characteristics were evaluated by sweeping a voltage of 0 to -80 V (Vg) to the gate electrode using a digital multimeter (SMU237, Keithley), and comparing the current Id between the source and drain electrodes applied with -80 V . As a result, the mobility was 5 × 10 ^-3 and the ON / OFF ratio was 10 ⁴ . The mobility was obtained from a slope of? Id-Vg by a well-known method. The unit is cm 2 / V · s. Further, the ON / OFF ratio is obtained by (the maximum value of the absolute value of Id) / (the minimum value of the absolute values of Id).

&Lt; Production of photoelectric conversion element and evaluation of photoelectric conversion characteristic >

150 mg of the dispersion of the phthalocyanine nano-sized structure (1), 45 mg of PCBM (manufactured by Frontier Carbon Co., Ltd.) and 200 mg of orthodichlorobenzene were charged into a sample bottle and ultrasonically irradiated for 30 minutes in an ultrasonic cleaner (47 kHz) (1) was obtained.

An ITO transparent conductive layer serving as an anode was deposited on the glass substrate by sputtering to a thickness of 100 nm, and the ITO transparent conductive layer was patterned on a strip of 2 mm width by photolithography-etching. The resulting patterned ITO glass substrate was subjected to ultrasonic cleaning three times for 15 minutes each in the order of a neutral detergent, distilled water, acetone and ethanol, followed by UV / ozone treatment for 30 minutes. A PEDOT: PSS aqueous dispersion (AI4083 Manufactured by HCS Tarck) was spin-coated to form a buffer layer 1 made of PEDOT: PSS on the ITO transparent electrode layer to a thickness of 60 nm. This was dried on a hot plate heated to 100 占 폚 for 5 minutes and then the photoelectric conversion layer material (1) was spin-coated on the PEDOT: PSS layer to obtain an organic semiconductor (1) Layer. Thereafter, the above-described "substrate on which the organic semiconductor layer was formed" and a deposition metal mask (for forming a rectangular pattern of 2 mm width) were provided in a vacuum evaporation apparatus, the degree of vacuum in the apparatus was increased to 5 × 10 ^-4 Pa, Aluminum to be a cathode was deposited and deposited to have a rectangular pattern of 2 mm in width by a heating method (film thickness: 80 nm). Thus, a photoelectric conversion element 1 having an area of 2 mm x 2 mm (a portion where the ITO layer on the strip and the aluminum layer intersect) was produced.

The positive and negative electrodes of the photoelectric conversion element 1 were connected to a digital multimeter (trade name: ADC1) (trade name, manufactured by ADC) to obtain a similar solar light having a spectrum shape of AM 1.5 and an irradiation intensity of 100 mW / (Sweeping) the voltage in the atmosphere from -0.1 V to +0.8 V under the irradiation of the simulator XES151S (product name, product name: Sanayaku Co., Ltd.) (measurement from the ITO layer side). The short-circuit current density (applied voltage, the value of current density when 0V days or less, J _sc) is applied to the value of the voltage when the 4.93㎃ / ㎠, the open end voltage (current density is zero. Or less, V _oc ) Was 0.56 V, and the fill factor (FF) was 0.37. The photoelectric conversion efficiency PCE calculated from these values was 1.01%. FF and PCE were calculated by the following equations.

FF = JV _max / (J _sc x V _oc )

(Where JV _max is a product of the current density and the applied voltage at a point where the product of the current density and the applied voltage becomes maximum between the applied voltage of 0 V and the open-ended voltage value)

PCE = [(J _sc x V _oc x FF) / similar solar light intensity (100 mW / cm 2)] x 100 (%)

(Example 2)

&Lt; Preparation of dispersion of phthalocyanine nano size structure and phthalocyanine nano size structure >

A phthalocyanine nano size structure dispersion (2) was obtained in the same manner as in Example (1), except that the sulfamoyl group substituted phthalocyanine obtained in Synthesis Example (2) was used as the phthalocyanine having a substituent.

&Lt; Evaluation of transistor fabrication and transistor characteristics (mobility)

A transistor (2) was obtained as the embodiment (1) except that the above-mentioned phthalocyanine nano-size structure dispersion (2) was used in the dispersion of the phthalocyanine nano size structure. The evaluation results of the characteristics are summarized in Table 1.

(Example 3)

&Lt; Preparation of dispersion of phthalocyanine nano size structure and phthalocyanine nano size structure >

A phthalocyanine nano size structure dispersion (3) was obtained in the same manner as in Example (1), except that the sulfamoyl group substituted phthalocyanine obtained in Synthesis Example (3) was used as the phthalocyanine having a substituent.

&Lt; Evaluation of transistor fabrication and transistor characteristics (mobility)

A transistor (3) was obtained as the embodiment (1) except that the above-mentioned phthalocyanine nano size structure dispersion (3) was used in the dispersion of the phthalocyanine nano size structure. The evaluation results of the characteristics are summarized in Table 1.

(Example 4)

&Lt; Preparation of dispersion of phthalocyanine nano size structure and phthalocyanine nano size structure >

A phthalocyanine nano size structure dispersion (4) was obtained in the same manner as in Example (1), except that the sulfamoyl group substituted phthalocyanine obtained in Synthesis Example (4) was used as a phthalocyanine having a substituent.

&Lt; Evaluation of transistor fabrication and transistor characteristics (mobility)

A transistor (4) was obtained as the example (1) except that the above-mentioned phthalocyanine nano-size structure dispersion (4) was used in the dispersion of the phthalocyanine nano size structure. The evaluation results of the characteristics are summarized in Table 1.

(Example 5)

&Lt; Preparation of dispersion of phthalocyanine nano size structure and phthalocyanine nano size structure >

A phthalocyanine nano size structure dispersion (5) was obtained in the same manner as in Example (1), except that the sulfamoyl group substituted phthalocyanine obtained in Synthesis Example (5) was used as the phthalocyanine having a substituent.

&Lt; Evaluation of transistor fabrication and transistor characteristics (mobility)

A transistor (5) was obtained as the embodiment (1) except that the phthalocyanine nano size structure dispersion (5) was used for the dispersion of the phthalocyanine nano size structure. The evaluation results of the characteristics are summarized in Table 1.

(Example 6)

&Lt; Preparation of dispersion of phthalocyanine nano size structure and phthalocyanine nano size structure >

A phthalocyanine nano size structure dispersion (6) was obtained in the same manner as in Example (1), except that the sulfamoyl group substituted phthalocyanine obtained in Synthesis Example (6) was used as the phthalocyanine having a substituent.

&Lt; Evaluation of transistor fabrication and transistor characteristics (mobility)

A transistor 6 was obtained as the embodiment (1) except that the above-mentioned phthalocyanine nano size structure dispersion (6) was used in the dispersion of the phthalocyanine nano size structure. The evaluation results of the characteristics are summarized in Table 1.

(Example 7)

&Lt; Preparation of dispersion of phthalocyanine nano size structure and phthalocyanine nano size structure >

A phthalocyanine nano size structure dispersion (7) was obtained in the same manner as in Example (1), except that the sulfamoyl group substituted phthalocyanine obtained in Synthesis Example (7) was used as the phthalocyanine having a substituent.

&Lt; Evaluation of transistor fabrication and transistor characteristics (mobility)

Transistor (7) was obtained as Example (1) except that the above-mentioned phthalocyanine nano size structure dispersion (7) was used in the dispersion of the phthalocyanine nano size structure. The evaluation results of the characteristics are summarized in Table 1

(Example 8)

&Lt; Preparation of dispersion of phthalocyanine nano size structure and phthalocyanine nano size structure >

A phthalocyanine nano size structure dispersion (8) was obtained in the same manner as in Example (1), except that the sulfamoyl group substituted phthalocyanine obtained in Synthesis Example (8) was used as the phthalocyanine having a substituent.

&Lt; Evaluation of transistor fabrication and transistor characteristics (mobility)

A transistor 8 was obtained as the embodiment (1) except that the phthalocyanine nano size structure dispersion (8) was used for the dispersion of the phthalocyanine nano size structure. The evaluation results of the characteristics are summarized in Table 1.

(Comparative Example 1)

The sulfamoyl group-substituted phthalocyanine of [Chemical Formula 19] was synthesized by the method described in WO2010 / 122921.

[19]

In the above compound, Q represents a hydrogen atom or a methyl group, and has an average value of propylene oxide / ethylene oxide = 29/6 (molar ratio), n = 35, and an average value of m = 1.2.

A phthalocyanine nano size structure dispersion (1) 'was obtained in the same manner as in Example (1) except that the sulfamoyl group substituted phthalocyanine represented by [Chemical Formula 19] was used as a phthalocyanine having a substituent.

&Lt; Evaluation of transistor fabrication and transistor characteristics (mobility)

Transistor (1) 'was obtained as Example (1) except that the above-mentioned phthalocyanine nano size structure dispersion (1) was used in the dispersion of the phthalocyanine nano size structure. The evaluation results of the characteristics are summarized in Table 1.

(Comparative Example 2)

A phthalocyanine nano size structure dispersion (2) 'was obtained in the same manner as in Example (1), except that the phthalocyanine derivative represented by the formula [20] was used as the phthalocyanine having a substituent. Regarding the adjustment of the dispersion, the method described in WO2010 / 122921 was followed.

[20]

&Lt; Evaluation of transistor fabrication and transistor characteristics (mobility)

A transistor (2) 'was obtained as the example (1) except that the phthalocyanine nano size structure dispersion (2)' was used in the dispersion of the phthalocyanine nano size structure. The evaluation results of the characteristics are summarized in Table 1.

[Table 1]

According to the phthalocyanine nano-sized structure of the present invention, it is possible to construct an electronic device (transistor or the like) having improved characteristics in order to use a phthalocyanine derivative having an optimized structure in the material constituting the phthalocyanine nano-sized structure.

One… Board
2… Electrode a
3 ... Photoelectric conversion layer
4… Electrode b
5 ... The layer containing the phthalocyanine nano-sized structure of the present invention (in the case of the electrode a being the anode) or the layer containing the electron-accepting material (in the case of the electrode a being the cathode)
6 ... A layer containing an electron-accepting material (when the electrode b is a cathode) or a layer containing the phthalocyanine nano-size structure of the present invention (when the electrode b is an anode)
7 ... Board
8… Gate electrode
9 ... Gate insulating film
10 ... Source electrode
11 ... Drain electrode
12 ... The semiconductor layer containing the phthalocyanine nano size structure of the present invention

Claims (9)

A nano-sized structure containing an unsubstituted phthalocyanine and a phthalocyanine having a substituent,
The shape of the structure has a long diameter and a short diameter, a short diameter is 500 nm or less,
Wherein the unsubstituted phthalocyanine is represented by the general formula (1) or (2)

X is a group selected from the group consisting of a copper atom, a zinc atom, a cobalt atom, a nickel atom, a tin atom, a lead atom, a magnesium atom, an iron atom, a palladium atom, a calcium atom, GeO, TiO, VO, and AlCl Which is selected)
A phthalocyanine nano-sized structure wherein the phthalocyanine having a substituent is represented by the general formula (3) or (4).

X is a group selected from the group consisting of a copper atom, a zinc atom, a cobalt atom, a nickel atom, a tin atom, a lead atom, a magnesium atom, an iron atom, a palladium atom, a calcium atom, GeO, TiO, VO, and AlCl Which is selected,
Each hydrogen atom in the benzene ring of the phthalocyanine skeleton may be substituted with fluorine, chlorine, bromine, and Z ₁ to Z ₈ each independently represent a hydrogen atom, a noncyclic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent , A, b, c, and d each independently represent an integer of 0 to 4, provided that at least one of them is a divalent linking group selected from the group consisting of 0 , And when Z _{1 to} Z ₈ are the general formula (5) or (6), and both are hydrogen atoms.

(Wherein q is an integer of 4 to 100, each Q is independently a hydrogen atom or a methyl group, and Q 'is a non-cyclic hydrocarbon group having 1 to 30 carbon atoms)

(Wherein m is an integer of 1 to 20, and R and R 'each independently represent an alkyl group having 1 to 20 carbon atoms) The method according to claim 1,
Z _{1 to} Z ₈ are a group selected from the group consisting of a non-cyclic or cyclic alkyl group having _{1 to} 22 carbon atoms, a phenyl group, a thienyl group, and the following groups (7) to (12).

(Wherein R ₁ and R ₂ represent an alkyl group having 1 to 4 carbon atoms) 3. The method of claim 2,
The non-cyclic or cyclic alkyl group having 1 to 22 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- N-heptyl group, n-heptyl group, n-heptyl group, n-heptyl group, n-octyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-docosyl group and cyclohexyl group. An ink composition comprising the phthalocyanine nano-size structure according to any one of claims 1 to 3 and an organic solvent as essential components. An electronic device comprising the phthalocyanine nano-size structure according to any one of claims 1 to 3. A transistor comprising the channel portion of the phthalocyanine nano-size structure according to any one of claims 1 to 3. The method for manufacturing a transistor according to claim 6, wherein the channel part is formed by forming the ink composition according to claim 4. A photoelectric conversion element having at least an anode and a cathode,
A photoelectric conversion element comprising a film containing a phthalocyanine nano-sized structure according to any one of claims 1 to 3 between an anode and a cathode. The method for manufacturing a photoelectric conversion element according to claim 8, further comprising a step of forming the ink composition according to claim 4 between the anode and the cathode.

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